WO2006016672A1 - Film siliceux comportant un décalage plus petit de bande plate et procédé de fabrication de celui-ci - Google Patents

Film siliceux comportant un décalage plus petit de bande plate et procédé de fabrication de celui-ci Download PDF

Info

Publication number
WO2006016672A1
WO2006016672A1 PCT/JP2005/014819 JP2005014819W WO2006016672A1 WO 2006016672 A1 WO2006016672 A1 WO 2006016672A1 JP 2005014819 W JP2005014819 W JP 2005014819W WO 2006016672 A1 WO2006016672 A1 WO 2006016672A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum
siliceous film
perhydropolysilazane
group
compound
Prior art date
Application number
PCT/JP2005/014819
Other languages
English (en)
Japanese (ja)
Inventor
Yasuo Shimizu
Masaaki Ichiyama
Teruno Nagura
Original Assignee
Az Electronic Materials (Japan) K.K.
Az Electronic Materials Usa Corp.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Az Electronic Materials (Japan) K.K., Az Electronic Materials Usa Corp. filed Critical Az Electronic Materials (Japan) K.K.
Priority to US11/629,592 priority Critical patent/US20070259106A1/en
Priority to EP05780260.5A priority patent/EP1785459B1/fr
Publication of WO2006016672A1 publication Critical patent/WO2006016672A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
    • H01L21/02145—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing aluminium, e.g. AlSiOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H01L21/3121—Layers comprising organo-silicon compounds
    • H01L21/3125—Layers comprising organo-silicon compounds layers comprising silazane compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604—Deposition from a gas or vapour
    • H01L21/31616—Deposition of Al2O3
    • H01L21/3162—Deposition of Al2O3 on a silicon body
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2

Definitions

  • the present invention relates to a method for producing a siliceous film. More specifically, the present invention relates to a method for producing a siliceous film having a small flat band shift value and excellent insulating properties.
  • an electronic device such as a semiconductor device
  • semiconductor elements such as transistors, resistors, and the like are arranged on a substrate. These must be electrically insulated. Therefore, a region for separating the elements is necessary between these elements, and this is called an isolation region.
  • a siliceous film is generally used as a material for forming such an isolation region.
  • the siliceous film produced by these methods has a flat band shift of the CV curve due to residual nitrogen, carbon, and hydrogen, which is thought to be caused by the raw material polysilazane and solvent.
  • the siliceous film formed by the method there is room for improvement in the insulation properties that are high.
  • the heating temperature is required to be kept low by limiting the heat resistance and oxidation resistance of the substrate to be applied, the residual nitrogen, carbon, or hydrogen tends to increase.
  • Patent Document 1 Patent No. 3511024
  • Patent Document 2 Japanese Patent No. 3178412
  • Patent Document 3 JP-A-8-5963
  • Patent Document 4 Japanese Patent Application Laid-Open No. 11 105185
  • Patent Document 5 JP-A-4 63833
  • Patent Document 6 JP-A-9 31333
  • Patent Document 7 Japanese Patent Application Laid-Open No. 8-176511
  • Patent Document 8 JP-A-8-176512
  • Patent Document 9 JP-A-5-345826
  • the present invention solves such problems and provides a method for producing a siliceous film having a small flat band shift value, that is, excellent electrical characteristics such as insulating characteristics.
  • the coating composition according to the present invention has a number average molecular weight of 100 to 50,000, a group strength including a perhydropolysilazane and a modified perhydropolysilazane.
  • the selected one or more polysilazane compounds, an aluminum compound, and the aluminum content is not less than lOppb and not more than lOOppm in terms of a molar ratio of aluminum atoms to silicon atoms contained in the polysilazane compound.
  • the method for producing a siliceous film according to the present invention includes at least one polysilazane salt having a number average molecular weight of 100 to 50,000, wherein perhydropolysilazane and modified perhydropolysilazane force are also selected.
  • a coating solution containing a compound, an aluminum compound, and a solvent, and having an aluminum content of not less than lOppb and not more than lOOppm in terms of a mole ratio of aluminum atoms to silicon atoms contained in the polysilazane compound is applied to the substrate. And firing in an atmosphere containing water vapor, oxygen, or a mixed gas thereof.
  • the siliceous film according to the present invention is a siliceous film obtained by applying a coating liquid containing a polysilazane compound and an aluminum compound to a substrate and baking it in an oxidizing atmosphere.
  • the aluminum content is characterized in that the molar ratio of aluminum atoms to silicon atoms is not less than lOppb and not more than lOOppm.
  • the invention's effect it is possible to produce a siliceous film having a small flat band shift value, whereby a semiconductor element having excellent electrical characteristics, for example, an element isolation film or a gate insulating film having excellent insulating characteristics. A film can be formed.
  • perhydropolysilazane or modified perhydropolysilazane can also be used as needed.
  • One or more polysilazane compounds can be used as needed.
  • perhydropolysilazane is represented by the following general formula (I).
  • n is a number representing the degree of polymerization.
  • a modified perhydropolysilazane obtained by modifying the perhydropolysilazane of the general formula (I) with a silazane compound, alcohol, or amine can be used.
  • perhydropolysilazane is preferably used in order to reduce the flat band shift of the siliceous film obtained using the coating composition. This is because when a polysilazane compound containing a relatively large amount of organic groups that contains organic groups other than hydrogen in the main chain is used, atoms such as carbon derived from the organic groups are contained in the siliceous film. This is because the effect of the present invention may be reduced.
  • a modified perhydropolysilazane obtained by modifying a part of perhydropolysilazane from the viewpoints of the coating property of the coating solution during production, stability during storage, and the like.
  • the compound that modifies perhydropolysilazane include compounds such as hexamethyldisilazane, methyl alcohol, ethyl alcohol, and ethylenediamine.
  • a modified perhydropolysilazane can be obtained by substituting a part of hydrogen of perhydropolysilazane, particularly terminal hydrogen, using these.
  • modified perhydropolysilazanes are described in Patent Documents 5 to 9.
  • the weight average molecular weight of the perhydropolysilazane or modified perhydropolysilazane used in the coating composition according to the present invention is determined by the coating property of the coating composition, particularly when coated by spin coating. From the perspective of 100-50, 00 0, preferred ⁇ is 500 to 20,000.
  • these polysilazane compounds are dissolved in a solvent.
  • the solvent used at this time is preferably an inert organic solvent without active hydrogen.
  • organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, jetylbenzene, trimethylbenzene, and triethylbenzene; cyclohexane, cyclohexene, decahydronaphthalene, and ethylcyclohexane.
  • Aliphatic hydrocarbon solvents such as xane, methylcyclohexane, p-menthane, dipentene (limonene), pinene; n pentane, i pentane, n-hexane, i monohexane, n-heptane, i-heptane, n Octane, i-octane, n-nonane, i-nonane, n-decane, saturated hydrocarbon compounds such as decane, ether solvents such as dipropyl ether and dibuchel ether; ketone solvents such as methyl isobutyl ketone; propylene And ester solvents such as glycol monomethyl ether acetate It is. Of these, those capable of sufficiently dissolving the aluminum compound described later are particularly preferred.
  • the aluminum compound that can be used in the present invention is not particularly limited, but is preferably dissolved in the polysilazane solution. Therefore, it can be appropriately selected depending on the solvent used in the coating composition.
  • the aluminum compound that can be used in the present invention can be represented, for example, by the following general formula.
  • ⁇ , And Zeta 3 are each independently hydrogen, a hydroxyl group, a halogen atom, alkyl group, cycloalkyl group, Ariru group, Aruke - group, Shikuroaruke - group, an alkoxy group, also selected ⁇ cetyl ⁇ Seth sulfonate functionalized Group, And 2 or 3 of ⁇ 3 may form a cyclic structure. Further, ⁇ ⁇ ⁇ 2 and ⁇ 3 may be an organic group including a key element.
  • the aluminum compounds in the present invention are preferably those represented by the following general formulas ( ⁇ -1) to ( ⁇ -3).
  • R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, and X 1 , X 2 , and X 3 are each independently Fluorine, chlorine, or iodine.
  • examples of the aluminum compound used in the present invention include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tri-n-propoxyaluminum, trimethylaluminum, triethylaluminum, triisopropylaluminum. -Um, tri-n-propylaluminum, aluminum fluoride, aluminum chloride, aluminum iodide, triacetylacetonate aluminum, triethylacetoacetate aluminum, and others.
  • an aluminum compound containing silicon such as di-s-butoxyaluminoxy-triethoxysilane, can be used.
  • the amount of applied force of these aluminum compounds is not particularly limited as long as the effects of the present invention are not impaired.
  • the molar ratio of the aluminum atom to the silicon atom contained in the polysilazane compound is ⁇ pb or more, preferably lOOppb or more. More preferred.
  • the molar ratio of the aluminum atom to the silicon atom contained in the polysilazane compound is preferably lOOppm or less, and more preferably lOppm or less. Note that the amount of aluminum compound added is much smaller than that described in Patent Document 3 or 4, and silica obtained by such a small amount of aluminum compound is used. It was surprising that the properties of the membrane were dramatically improved.
  • the aluminum compound can be added to the coating composition by any method. Specifically, a solid aluminum compound can be added and dissolved in the coating composition, or the aluminum compound can be dissolved in a solvent and mixed with the coating composition. When the aluminum compound is dissolved in a solvent, a solvent that can be used when dissolving the polysilazane compound can be used. At this time, the solvent used for dissolving the polysilazane compound may be different from the solvent used for preparing the aluminum compound solution.
  • Aluminum- There are no particular restrictions on the temperature or pressure when adding the sulfur compound, but generally 0 to 200 ° C.
  • the method for producing a siliceous film according to the present invention comprises applying the above-described coating composition to a substrate.
  • the siliceous film is formed by firing.
  • the surface material of the substrate used is not particularly limited, and examples thereof include bare silicon and a silicon wafer on which a thermal acid film or a silicon nitride film is formed as required. If necessary, a structure such as a trench isolation groove may be formed on the substrate.
  • Examples of methods for applying the coating composition to the substrate surface include conventionally known methods such as spin coating, dipping, spraying, and transfer.
  • the coating film formed on the substrate surface is baked in an atmosphere containing water vapor, oxygen, or a mixed gas thereof, that is, in an oxidizing atmosphere.
  • an inert gas such as nitrogen or helium may be mixed in the atmosphere as long as the effects of the present invention are not impaired.
  • the firing conditions are preferably carried out under relatively strong acidic conditions in order to minimize impurity elements remaining in the siliceous film, for example, carbon, hydrogen, nitrogen and the like. .
  • the oxygen content is preferably 1% or more based on volume.
  • the method of the present invention when firing is performed in an atmosphere containing water vapor, it is preferably 0.1% or more based on the volume, more preferably 1% or more. . In the present invention, it is particularly preferable to perform firing in a mixed gas atmosphere containing oxygen and water vapor.
  • the firing temperature needs to be a temperature at which the polysilazane compound can be added to the siliceous film. Generally 100 to 1,200. C, preferred ⁇ is 300 ⁇ 1,000. Baking with C. Here, the lower the firing temperature, the more prominent the flat band shift improving effect is compared to the conventional manufacturing method. In addition, the higher the firing temperature, the smaller the flat band shift tends to obtain a siliceous film having excellent electrical characteristics.
  • the firing time is a force that can be appropriately selected depending on the firing temperature, and is generally 5 minutes to 10 hours. Here, from the viewpoint of production efficiency in production, it is preferably 1 hour or less.
  • the siliceous film produced by the production method according to the present invention has a small flat band shift value. Such characteristics are presumably because aluminum oxide derived from the aluminum compound is uniformly dispersed in the formed siliceous film. For this reason, the siliceous film according to the present invention is excellent in electrical characteristics, for example, insulation characteristics.
  • the siliceous film and the substrate with the siliceous film according to the present invention can be produced, for example, by the method described above.
  • the ratio of the aluminum atom in the aluminum compound used as a raw material and the key atom contained in the polysilazane compound does not change even in the finally obtained siliceous film.
  • the siliceous film of the present invention can be produced by setting the aluminum compound used in the production to have a ratio of aluminum atoms to silicon atoms of ⁇ pb or more and lOO ppm or less.
  • a siliceous film having a low aluminum content is formed, and aluminum atoms are introduced into the siliceous film by another means, for example, ion implantation, to obtain a final aluminum content.
  • ion implantation ion implantation
  • siliceous films or substrates with siliceous films have excellent electrical characteristics, and various semiconductor elements such as element isolation films, interlayer dielectric films such as premetal deelectric films and intermetal depolar films, liquid crystals It is useful as a gate insulating film for display devices
  • a reactor equipped with a gas blowing tube, a mechano-car stirrer and a single condenser was prepared in a four-necked flask with an internal volume of 2 liters. After the inside of the reactor was replaced with dry nitrogen, 1500 ml of dry pyridine was introduced into a four-necked flask and cooled on ice. Next, when dichlorosilane lOOg is added to pyridine, a white solid adduct (SiH CI-2C H N) is produced.
  • reaction mixture was further ice-cooled, and 70 g of ammonia was added to the reaction mixture while stirring. Blowed in. Subsequently, dry nitrogen was blown into the reaction mixture for 30 minutes to remove excess ammonia.
  • reaction mixture was filtered under reduced pressure using a Buchner funnel under a dry nitrogen atmosphere to obtain 1200 ml of a filtrate.
  • pyridine was distilled off with an evaporator to obtain 40 g of perhydropolysilazane.
  • the number average molecular weight in terms of polystyrene was 800.
  • the infrared absorption spectrum of this perhydropolysilazane was measured and found to have absorption based on N—H bonds of wave numbers (cm- 1 ) 3350 and 1180, absorption based on Si—H bonds of 2170, Si—N of 1020 to 820 — Absorption based on Si bond was observed.
  • a substrate in which a thermal oxidation film of lOnm was formed on a p-type silicon wafer having a diameter of 8 inches was prepared, and the polysilazane solution was formed on the substrate using a spin coater under conditions of main spin lOOOrpm Z20 seconds. Applied. After coating, the substrate was dried on a hot plate by heating at 150 ° CZ for 3 minutes. Subsequently, the substrate was heated to form a siliceous film having a thickness of 500 nm. The heating conditions were as follows.
  • Heating condition 1 Heated at 400 ° C for 15 minutes in an atmosphere with a water vapor concentration of 80 vol% and an oxygen concentration of 20 vol%.
  • Heating condition 2 Heated at 800 ° C for 15 minutes in an atmosphere with a water vapor concentration of 80 vol% and an oxygen concentration of 20 vol%.
  • Heating condition 3 Heated at 400 ° C for 15 minutes in an atmosphere with a water vapor concentration of 80 vol% and an oxygen concentration of 20 vol%, then further heated at 800 ° C for 30 minutes in a dry nitrogen atmosphere.
  • Heating condition 4 Heated at 400 ° C for 30 minutes in a nitrogen atmosphere.
  • a flat band shift was measured for each of the obtained substrates.
  • the thickness of each substrate was set to 5 using an ellipsometer (Model—M44 manufactured by JA Woolam).
  • the CV curve and the flat band shift value based on the CV curve were measured using an automatic mercury probe CVZIV measuring device (SSM495, manufactured by Nippon SSM Co., Ltd.).
  • the applied voltage for CV measurement was in the range of ⁇ 100 to + 100V.
  • the flat band value of the high-density plasma CVD film was measured in the same manner as in Comparative Example 1.
  • Tri (isopropoxy) aluminum lg was mixed with dehydrated dibutyl ether lOOg to obtain a tri (isopropoxy) aluminum solution.
  • the flat band value was measured in the same manner as in Example 1 except that tri (isopropoxy) aluminum was replaced with tri (acetylacetonate) aluminum and the addition amount of the aluminum compound solution was changed to 43 mg.
  • Example 1 is the same as Example 1 except that tri (isopropoxy) anolium was replaced with (ethinoreacetoacetate) di (isopropoxy) aluminum and the amount of added force of the aluminum compound solution was changed to 34 mg. Similarly, the flat band value was measured.
  • the flat band value was measured in the same manner as in Example 1 except that tri (isopropoxy) aluminum was replaced with tri (ethylacetoacetate) aluminum and the addition amount of the aluminum compound solution was replaced with 56 mg.
  • the flat band value was measured in the same manner as in Example 1 except that tri (isopropoxy) aluminum was replaced with di-s-butoxyaluminoxy-triethoxysilane and the addition amount of the aluminum compound solution was changed to 47 mg.
  • the flat band value was measured in the same manner as in Example 1 except that the amount of tri (isopropoxy) aluminum solution added to the polysilazane solution was changed to 2.7 g.
  • Example 1 3ppm -1 1.2-8.5-9.5 -38.2
  • Example 2 3ppm -10.0-6.2 -1 1.0 -44.0
  • Example 3 3ppm -9.3 -9.0 -10.1 -40.5
  • Example 4 3ppm -1 1.0 -7.8-10.2- 46.2
  • Example 5 «jppm -9.9 -7.2 -8.9 -39.5
  • Example 6 3ppm -10.4 -8.8 -10.4 -50.2 Comparative Example 3 3ppb -19.0 -13.4 -22.4
  • AI content is the atomic ratio of aluminum to key
  • the aluminum content of the siliceous film obtained under each firing condition was measured using a secondary ion mass spectrometer (type 6650 manufactured by Physical Electronics) and a stylus type surface shape.
  • a secondary ion mass spectrometer type 6650 manufactured by Physical Electronics
  • the aluminum content almost the same as the coating solution was measured, and the aluminum content of the coating composition was the siliceous film produced using the coating composition. It was found to be consistent with the aluminum content.
  • the aluminum content is constant in the thickness direction of the siliceous film, and it was found that aluminum atoms are uniformly distributed in the siliceous film.
  • the production method according to the present invention realizes a siliceous film having a small flat band shift value, that is, a siliceous film having excellent insulating properties.
  • the siliceous film produced by this production method is a semiconductor. It can be used as an element, for example, an element isolation film, an interlayer insulating film such as a pre-metal de-electric film or an inter-dielectric film, and a gate insulating film of a display device such as a liquid crystal.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Silicon Compounds (AREA)
  • Formation Of Insulating Films (AREA)
  • Paints Or Removers (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Laminated Bodies (AREA)

Abstract

Il est décrit un procédé de fabrication d'un film siliceux présentant d'excellentes caractéristiques d'isolement et une composition de revêtement utilisée pour celui-ci. En particulier, il est décrit une composition des revêtement contenant un perhydropolysilazane ou un perhydropolysilazane modifié présentant un poids moléculaire moyen en nombre de 100 à 50 000 et un composé d'aluminium présentant un rapport molaire des atomes d'aluminium sur les atomes de silicium qui n'est pas inférieur à 10 ppb et ne dépasse pas 100 ppm. Un film siliceux est produit en enduisant une telle composition de revêtement sur un substrat et en brûlant le substrat recouvert dans une atmosphère contenant de la vapeur d'eau, de l'oxygène ou un mélange gazeux de ceux-ci.
PCT/JP2005/014819 2004-08-13 2005-08-12 Film siliceux comportant un décalage plus petit de bande plate et procédé de fabrication de celui-ci WO2006016672A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/629,592 US20070259106A1 (en) 2004-08-13 2005-08-12 Polysilazane coating composition and siliceous film
EP05780260.5A EP1785459B1 (fr) 2004-08-13 2005-08-12 Film siliceux comportant un decalage plus petit de bande plate et procede de fabrication de celui-ci

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-235792 2004-08-13
JP2004235792A JP2006054353A (ja) 2004-08-13 2004-08-13 フラットバンドシフトの少ないシリカ質膜およびその製造法

Publications (1)

Publication Number Publication Date
WO2006016672A1 true WO2006016672A1 (fr) 2006-02-16

Family

ID=35839429

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/014819 WO2006016672A1 (fr) 2004-08-13 2005-08-12 Film siliceux comportant un décalage plus petit de bande plate et procédé de fabrication de celui-ci

Country Status (7)

Country Link
US (1) US20070259106A1 (fr)
EP (1) EP1785459B1 (fr)
JP (1) JP2006054353A (fr)
KR (1) KR20070044051A (fr)
CN (1) CN101001930A (fr)
TW (1) TWI389208B (fr)
WO (1) WO2006016672A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012117990A1 (fr) * 2011-03-01 2012-09-07 Ａｚエレクトロニックマテリアルズ株式会社 Composition pour la formation de film de faible indice de réfraction, procédé de formation de film de faible indice de réfraction et film de faible indice de réfraction et film antireflet tous deux formés par le procédé de formation
JP2013046009A (ja) * 2011-08-26 2013-03-04 Shin Etsu Chem Co Ltd 太陽電池及びその製造方法
WO2013077255A1 (fr) * 2011-11-24 2013-05-30 コニカミノルタ株式会社 Film de barrière vis-à-vis des gaz et dispositif électronique
KR101412453B1 (ko) * 2006-09-08 2014-06-30 에이제토 엘렉토로닉 마티리알즈 아이피 (재팬) 가부시키가이샤 실리카질 막 형성용 조성물 및 이를 사용한 실리카질 막의 제조법

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7563727B2 (en) 2004-11-08 2009-07-21 Intel Corporation Low-k dielectric layer formed from aluminosilicate precursors
JP4530980B2 (ja) * 2005-08-26 2010-08-25 東京応化工業株式会社 膜形成用材料およびパターン形成方法
US7718553B2 (en) 2006-09-21 2010-05-18 Asm Japan K.K. Method for forming insulation film having high density
US7923200B2 (en) * 2007-04-09 2011-04-12 Az Electronic Materials Usa Corp. Composition for coating over a photoresist pattern comprising a lactam
JP5069494B2 (ja) * 2007-05-01 2012-11-07 ＡｚエレクトロニックマテリアルズＩｐ株式会社 微細化パターン形成用水溶性樹脂組成物およびこれを用いた微細パターン形成方法
US7781352B2 (en) 2007-06-06 2010-08-24 Asm Japan K.K. Method for forming inorganic silazane-based dielectric film
US7651959B2 (en) 2007-12-03 2010-01-26 Asm Japan K.K. Method for forming silazane-based dielectric film
US7622369B1 (en) 2008-05-30 2009-11-24 Asm Japan K.K. Device isolation technology on semiconductor substrate
US7745077B2 (en) * 2008-06-18 2010-06-29 Az Electronic Materials Usa Corp. Composition for coating over a photoresist pattern
US8765233B2 (en) 2008-12-09 2014-07-01 Asm Japan K.K. Method for forming low-carbon CVD film for filling trenches
JP5172867B2 (ja) * 2010-01-07 2013-03-27 ＡｚエレクトロニックマテリアルズＩｐ株式会社 ポリシラザンを含むコーティング組成物
US8541053B2 (en) 2010-07-08 2013-09-24 Molecular Imprints, Inc. Enhanced densification of silicon oxide layers
TWI613835B (zh) * 2012-01-06 2018-02-01 日商日立化成股份有限公司 鈍化膜形成用組成物
KR101556672B1 (ko) 2012-12-27 2015-10-01 제일모직 주식회사 실리카계 절연층 형성용 조성물, 실리카계 절연층 형성용 조성물의 제조방법, 실리카계 절연층 및 실리카계 절연층의 제조방법
CN103910885A (zh) * 2012-12-31 2014-07-09 第一毛织株式会社 制备间隙填充剂的方法、用其制备的间隙填充剂和使用间隙填充剂制造半导体电容器的方法
US10316216B2 (en) * 2016-08-31 2019-06-11 Samsung Sdi Co., Ltd. Composition for forming silica layer, and silica layer
US11450526B2 (en) 2018-05-30 2022-09-20 Taiwan Semiconductor Manufacturing Co., Ltd. Cyclic spin-on coating process for forming dielectric material
KR102395487B1 (ko) * 2019-08-21 2022-05-06 삼성에스디아이 주식회사 실리카 막 형성용 조성물 및 실리카 막

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63191832A (ja) * 1986-09-26 1988-08-09 Toa Nenryo Kogyo Kk 新規ポリアルミノシラザン及びその製造方法
JPH01221466A (ja) * 1988-03-01 1989-09-04 Toa Nenryo Kogyo Kk コーティング用組成物及びコーティング方法
JPH06299118A (ja) * 1993-04-20 1994-10-25 Tonen Corp コーティング用組成物及びコーティング方法
JPH06306329A (ja) * 1993-02-24 1994-11-01 Tonen Corp コーティング用組成物及びコーティング方法
JPH07196986A (ja) * 1993-12-28 1995-08-01 Tonen Corp コーティング用組成物
JPH11105187A (ja) * 1997-09-30 1999-04-20 Tonen Corp 高純度シリカ質膜の形成方法及び高純度シリカ質膜
JPH11105185A (ja) * 1997-09-30 1999-04-20 Tonen Corp 低誘電率シリカ質膜
JP2001026415A (ja) * 1999-07-13 2001-01-30 Tonengeneral Sekiyu Kk 低誘電率多孔質シリカ質膜、半導体装置およびコーティング組成物
JP2002075982A (ja) * 2000-08-29 2002-03-15 Clariant (Japan) Kk 低誘電率多孔質シリカ質膜、半導体装置およびコーティング組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05243223A (ja) * 1992-02-28 1993-09-21 Fujitsu Ltd 集積回路装置の製造方法
US5747623A (en) * 1994-10-14 1998-05-05 Tonen Corporation Method and composition for forming ceramics and article coated with the ceramics
JP3178412B2 (ja) * 1998-04-27 2001-06-18 日本電気株式会社 トレンチ・アイソレーション構造の形成方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63191832A (ja) * 1986-09-26 1988-08-09 Toa Nenryo Kogyo Kk 新規ポリアルミノシラザン及びその製造方法
JPH01221466A (ja) * 1988-03-01 1989-09-04 Toa Nenryo Kogyo Kk コーティング用組成物及びコーティング方法
JPH06306329A (ja) * 1993-02-24 1994-11-01 Tonen Corp コーティング用組成物及びコーティング方法
JPH06299118A (ja) * 1993-04-20 1994-10-25 Tonen Corp コーティング用組成物及びコーティング方法
JPH07196986A (ja) * 1993-12-28 1995-08-01 Tonen Corp コーティング用組成物
JPH11105187A (ja) * 1997-09-30 1999-04-20 Tonen Corp 高純度シリカ質膜の形成方法及び高純度シリカ質膜
JPH11105185A (ja) * 1997-09-30 1999-04-20 Tonen Corp 低誘電率シリカ質膜
JP2001026415A (ja) * 1999-07-13 2001-01-30 Tonengeneral Sekiyu Kk 低誘電率多孔質シリカ質膜、半導体装置およびコーティング組成物
JP2002075982A (ja) * 2000-08-29 2002-03-15 Clariant (Japan) Kk 低誘電率多孔質シリカ質膜、半導体装置およびコーティング組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1785459A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101412453B1 (ko) * 2006-09-08 2014-06-30 에이제토 엘렉토로닉 마티리알즈 아이피 (재팬) 가부시키가이샤 실리카질 막 형성용 조성물 및 이를 사용한 실리카질 막의 제조법
WO2012117990A1 (fr) * 2011-03-01 2012-09-07 Ａｚエレクトロニックマテリアルズ株式会社 Composition pour la formation de film de faible indice de réfraction, procédé de formation de film de faible indice de réfraction et film de faible indice de réfraction et film antireflet tous deux formés par le procédé de formation
JP2013046009A (ja) * 2011-08-26 2013-03-04 Shin Etsu Chem Co Ltd 太陽電池及びその製造方法
WO2013077255A1 (fr) * 2011-11-24 2013-05-30 コニカミノルタ株式会社 Film de barrière vis-à-vis des gaz et dispositif électronique
JPWO2013077255A1 (ja) * 2011-11-24 2015-04-27 コニカミノルタ株式会社 ガスバリアーフィルム及び電子機器
US9520576B2 (en) 2011-11-24 2016-12-13 Konica Minolta, Inc. Gas barrier film and electronic apparatus

Also Published As

Publication number Publication date
EP1785459A1 (fr) 2007-05-16
KR20070044051A (ko) 2007-04-26
US20070259106A1 (en) 2007-11-08
TW200610056A (en) 2006-03-16
EP1785459B1 (fr) 2016-12-28
TWI389208B (zh) 2013-03-11
CN101001930A (zh) 2007-07-18
EP1785459A4 (fr) 2011-10-19
JP2006054353A (ja) 2006-02-23

Similar Documents

Publication Publication Date Title
WO2006016672A1 (fr) Film siliceux comportant un décalage plus petit de bande plate et procédé de fabrication de celui-ci
JP4225765B2 (ja) 低誘電率非晶質シリカ系被膜の形成方法および該方法より得られる低誘電率非晶質シリカ系被膜
EP2206746B1 (fr) Composition contenant un composé polysilazane qui peut fournir un film siliceux dense
US7381441B2 (en) Low metal porous silica dielectric for integral circuit applications
US5043789A (en) Planarizing silsesquioxane copolymer coating
US20020132408A1 (en) Asymmetric organocyclosiloxanes and their use for making organosilicon polymer low-k dielectric film
JP4471564B2 (ja) 低誘電率非晶質シリカ系被膜形成用塗布液および該塗布液の調製方法
WO2015087847A1 (fr) Perhydropolysilazane, composition contenant un perhydropolysilazane, et procédé pour former un film de silice en utilisant ladite composition
US20070108593A1 (en) Zeolite sol and method for preparing the same, composition for forming porous film, porous film and method for forming the same, interlevel insulator film, and semiconductor device
KR100569741B1 (ko) 나노다공성 실리카 박막용 폴리올-기초 전구체
WO2007072750A1 (fr) Liquide de revêtement permettant de former un film de revetement de silice amorphe a faible constante diélectrique et film de revetement de silice amorphe a faible constante diélectrique obtenu à partir dudit liquide de revêtement
KR100914395B1 (ko) 폴리실라잔, 그 합성 방법, 반도체 소자 제조용 조성물 및 그 반도체 소자 제조용 조성물을 이용한 반도체 소자의 제조 방법
US20090130862A1 (en) Multi-functional cyclic silicate compound, siloxane-based polymer prepared from the compound and process of producing insulating film using the polymer
US20100174103A1 (en) Material for forming silicon-containing film, and silicon-containing insulating film and method for forming the same
JP4473352B2 (ja) 低比誘電率シリカ系被膜、それを形成するための塗布液、その塗布液の調製方法
US20060134441A1 (en) Siloxane-based polymer and method for forming dielectric film using the polymer
US6872456B2 (en) Siloxane resins
KR20110023411A (ko) 반도체 소자의 절연막 형성용 조성물
JP2004307692A (ja) 多孔質膜形成用組成物、多孔質膜の製造方法、多孔質膜、層間絶縁膜及び半導体装置
JP3939408B2 (ja) 低誘電率シリカ質膜
JP2004269692A (ja) 多孔質膜形成用組成物、多孔質膜の製造方法、多孔質膜、層間絶縁膜、及び半導体装置
JP2004292642A (ja) 多孔質膜形成用組成物、多孔質膜の製造方法、多孔質膜、層間絶縁膜、及び半導体装置
US20030064254A1 (en) Siloxane resins
KR100824037B1 (ko) 절연막 형성용 기공형성제 조성물, 이를 포함하는 절연막형성용 조성물, 이를 이용한 절연막의 제조 방법, 및이로부터 제조되는 절연막
KR20210031595A (ko) 규소 화합물 및 이를 사용하여 막을 증착시키는 방법

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 11629592

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 200580026893.6

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2005780260

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2005780260

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1020077005843

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2005780260

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWP Wipo information: published in national office

Ref document number: 11629592

Country of ref document: US